Electrochemistry

Dr.L.Cindrella
Professor (HAG)
Gibbs Free Energy ( Concept central to Chemical conversions)
 The combination of entropy, temperature and enthalpy
explains whether a reaction is going to be spontaneous or
not.
 "Free" energy refers to the amount of energy available to do
work once you have paid your price to entropy.

ΔG0 = ΔH0 − TΔS0

 When ΔG is negative, it indicates that a reaction or process

is spontaneous.
 A positive ΔG indicates a non-spontaneous reaction.

ΔG 0  RTlnK eq
ΔG 0  nFE 0
2
 Electrode, Electrode potential and its origin

Electrode: A metal
Electrical double layer
dipped in a solution of
giving rise to electrode
its own ion. Eg. Cu in
potential
CuSO4 solution

Electrochemical Series
 Measurement of electrode potential
• By connecting the electrode under test with the standard hydrogen
electrode, the value is measured by Poggendorff compensation
method
• Poggendorff compensation method is used for the measurement of
emf of electrochemical cells. This method has the advantage of giving
the emf of an open circuit when it produces no current and thus
determines emf of cells under reversible condition.
In this method, the unknown e.m.f. of a cell is opposed by a cell of
known e.m.f. and hence the name compensation method. The potential
difference between the two electrodes in a galvanic cell is called a cell
potential or emf of the cell. It is measured in volts. The electrical circuit
used is known as a potentiometer circuit.

AB is a wire of uniform resistance. The ends A and B
of the wire are connected to the two electrodes of a
lead storage battery C, through a variable
resistance, R. Along the wire AB there is a gradual
fall of potential which is proportional to the length of
the wire. One electrode of the cell, E, whose e.m.f is
to be measured, is connected through a
galvanometer, G to A. The other electrode is
connected through a key, K, to AB by a sliding
contact D. The potential difference between the
anode and cathode is called the EMF of the cell.
After pressing the key K the contact D
is moved along the wire until there is
no deflection of the galvanometer,
indicating that no current is flowing. At
this position the fall of potential along
the wire AB from A to D is equal to the
potential of the cell E. If now the cell E
is replaced by a standard cell, the
potential of which is very accurately
known, a new position of the contact,
D’, is found when no current flows
through the galvanometer. At this
position –
(Length of the wire with cell E)/( Length
of the wire with standard cell S) =
(Potential of the cell E)/(Potential of the
standard cell S)
From the known value of the potential
of the standard cell, S, and the
experimentally determined value of the
lengths of wire, the potential of the cell,
E, may be obtained.
Applications of EMF measurement
1. Determination of equilibrium constant
2. Determination of solubility of sparingly soluble salt
3. Determination of valency of ions in doubtful cases
4. Determination of thermodynamic functions
5. Determination of pH of a solution
6. Determination of activity coefficient
7. Determination of transference number
8. Potentiometric titrations
1. ln(keq ) = -nFE0/RT
2. Ag, AgCl;0.01N KCl | Saturated NH4NO3│0.01N AgNO3, Ag
𝑹𝑻 𝟎. 𝟎𝟏
𝑬= 𝒍𝒏
𝑭 𝑪
Where C is the concentration f Ag+ ions furnished by AgCl in KCl solution.
Ksp = [Ag+][Cl-] =C x 0.01; Solubility = C  0.01molL1

3. M| Mn+(c1)||Mn+(c2) |M
𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑪𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝒍𝒏
𝒏𝑭 𝑪𝟏
The value of n, the number of electrons involved in the cell reaction or the valency of the ions
can be calculated.
Hg| Mercurous nitrate(c1)||Mercurous nitrate (c2) |Hg
4. nFE0 = - ∆G0 = - (∆H0 – T ∆S0 )
5. pH  Ecell (By forming a cell with Std hydrogen electrode and hydrogen electrode containing
0.0592V the solution whose pH is to be measured.)
Nernst Equation

G RT  ar 
0
ar – activity of the reactant
E  ln ap – activity of the reactant
nF nF  a p 

Variables:

1.Temperature
2.Pressure
3.Concentration
 Concentration cells
Concentration cells of the first kind
• Consist of two electrodes of the same material in different activities, immersed in the same
electrolyte.
• An example is the amalgam cells, in which the electrodes differ only in the activity of the
metal dissolved in the amalgams.
M (𝒂𝟏 ), Hg│MA│M (𝒂II), Hg
• If aI > aII, the metal dissolves at the left-hand electrode and passes into the solution as the
corresponding ions:
MHg (𝒂I) ⇌ M2+ + 2e + Hg
• The opposite reaction will take place at the right-hand electrode:
M2+ + 2e + Hg ⇌ MHg (𝒂II)
• The overall process in the cell is the transfer of the metal from the concentrated amalgam to
the dilute one:
MHg (𝒂I) → MHg (𝒂II)
• The emf of such cell is calculated from Nernst equation as following:
𝑹𝑻 𝒂𝑰
𝑬= 𝒍𝒏
𝟐𝑭 𝒂𝑰𝑰
Electrolyte concentration cells
Zn, Zn2+(𝒂+)1 | Zn2+(𝒂+)2 , Zn
RHE: Zn2+(𝒂+)2 + 2e⇌ Zn(s)
LHE: Zn(s) ⇌ Zn2+(𝒂+)1 + 2e
Overall: Zn2+(𝒂+)2 ⇌ Zn2+(𝒂+)1
Substituting activity by molality r x m
Then we have the emf as:

𝑹𝑻 𝒓𝟐 𝒎𝟐
𝑬= 𝒍𝒏
𝑭 𝒓 𝟏 𝒎𝟏
 Gas cells
The two electrodes are of the same gas at different pressures.
The emf of the cell can be determined from the mechanical work done in
transferring one mole of the gas from the high pressure (P’) to the low pressure
(P):

𝑅𝑇 𝑃′
𝐸= ln
𝑧𝐹 𝑃
Hydrogen cell

𝐏𝐭, 𝑯𝟐 (𝐏’𝑯𝟐 ) │𝐇𝐂𝐥│𝑯𝟐 (𝑷𝑯𝟐 ), 𝐏𝐭

The emf is given by the equation:

𝑹𝑻 𝑷′𝑯𝟐
𝑬= 𝒍𝒏
𝒛𝑭 𝑷𝑯𝟐

 Hydrogen gas is ionized at the left-hand electrode. H2 (P’) ⇌ 2H+ + 2e

 Hydrogen ions are discharged and transferred to gas phase at the right-hand electrode.
2H+ + 2e ⇌H2 (P)
 The positive electric current flows within the cell from left to right.

𝑹𝑻 𝐏’𝑯𝟐 𝐏’𝑯𝟐
𝑬= 𝟐𝑭
𝒍𝒏 𝑷 = 0.02955 log 𝑷𝑯𝟐
𝑯𝟐
 Chlorine cell
Cl2 (𝑷′𝑪𝒍𝟐 ), Pt│HCl│Cl2 (𝑷𝑪𝒍𝟐 ), Pt
The emf is:

′
𝑹𝑻 𝑷𝑪𝒍 𝟐
𝑬= − 𝒍𝒏
𝒛𝑭 𝑷𝑪𝒍𝟐

 If P’ > P, then ionization of chlorine gas takes place at the left-hand electrode.
 At the right-hand electrode, the chlorine ions are discharged forming chlorine gas.
 The positive current flows within the cell from right to lift.
 The emf of the cell is negative.
Concentration cells of the second kind
• These cells consist of two electrodes of the same metal immersed in the same electrolyte of
different activities.
• It may be cationic or anionic depending on the ions with respect to which the electrodes are
reversible.
The following cell is an example for cationic cell:
K, Hg│KCl (𝒂II) | KCl (𝒂I)│K, Hg
and the following is anionic cell:
Ag, AgCl│HCl (𝒂II) | HCl (𝒂I)│AgCl, Ag
Where aI > aII.
• The overall process takes place in such cell is the transformation of the electrolyte from the
concentrated solution to the dilute one.
 Such cells are called also concentration cells with transference (or transport).
They may be known also as concentration cells with a liquid junction.
There is a boundary between the two solutions across which ions are transported and a diffusion
potential develops.
 The junctions can be classified into three distinct types:
• Two solutions of the same electrolyte with different concentrations, e.g.
H2, Pt │HCl (a1) | НС1 (a2) │Pt, H2
with the partial pressures of hydrogen equal on the two sides.
• Two solutions of the same concentration of one of the ions, but the other ion differs.
• Other cases.
The total cell potential is
Ecell = ENernst + Ej
where Ej is the liquid junction potential.
Transport number
• The electrical current is transported through the solution by the movement of the ions.
• The cations carry the positive charge to the negative electrode and the anions carry the negative
charge to the positive electrode.
• Thus, the total current passes through the solution (I) is divided between positive and negative ions.
• In some cases, one has to know the fraction of the total current carried by a particular ionic species.
• This value is known as the transport number or the transfer number of positive (t+) or negative (t-)
ions.
• The transport number can be defined as:
t+ = I+/I for positive ions
t- = I-/I for negative ions
For binary electrolyte we can write the transport number in terms of ionic motilities (conductance) as:
𝝀𝒐+
𝒕+ = 𝝀𝒐+ + 𝝀𝟎−
for positive ions

𝝀𝒐−
𝒕− = for negative ions.
𝝀𝒐+ + 𝝀𝟎−

Where 𝝀𝒐 is the equivalent (molar) conductance at zero concentration which is the same at infinite dilution (𝝀𝒐 = 𝝀∞)

It is obvious that:
𝝀𝒐+ + 𝝀𝟎− = 𝟏
For any electrolyte as well as for solutions containing several electrolytes, the transport number of an ionic species (I)
is expressed by the equation:
𝑰𝒊
𝒕𝒊 = and in this case:
𝑰𝒊

𝒕𝒊 = 𝟏
Liquid junction potential
• Liquid junction potentials are the result of different cation and anion mobilities under the
influence of an electric field.
• The potential manifests itself in the interface between two different solutions separated by a
porous separator or by a membrane.
Consider, for example, a porous membrane separating solutions of 0.1 M HCl and 0.01 M HCl.
• Because the concentration of HCl on the membrane’s left
side is greater than that on the right side of the
membrane, H+ and Cl– diffuse in the direction of the
arrows.
• The mobility of H+, however, is greater than that for Cl–.
• Thus, the solution on the right side of the membrane has
an excess of H+ and a positive charge.
• Simultaneously, the solution on the membrane’s left side
develops a negative charge due to the excess
concentration of Cl–.
• This difference in potential across the membrane is called
a junction potential, which is represented as Ej.
Salt bridge
• Used to eliminate the junction
potential of the cell.
• It is a u-shaped tube contains a
solution of an electrolytic salt.
• It is placed Inverted so as each tip is
immersed in one electrolyte of the
cell.

• So, it provides an ionic connection between the two electrolytes.

• two junction potentials are developed at both tips of the bridge with the same magnitude and
reverse sign.
• Thus, the overall junction potential is zero.
 EMF of the concentration cells of the second kind
Anionic cells
Ag, AgCl│HCl (𝒂 I) | HCl (𝒂II) │AgCl, Ag
• If aI > aII, the silver electrode on the left side which is in contact with the higher Cl- concentration is the anode.
• Thus, the reaction at the left-hand electrode is the dissolution of silver metal as a result of its combination with Cl-
ions:
Ag + Cl- (I) ⇌ AgCl + e
• Cl- ions are generated in the left side by the cathodic reaction:
AgCl + e ⇌ Ag + Cl- (II)
• The overall reaction is transport of Cl- from the left higher concentration to the right lower one:
Cl- (I) ⇌ Cl- (II)
• The emf of such cell is:
𝑹𝑻 𝒂𝑰 𝑯𝑪𝒍
𝑬= 𝐥𝐧
𝑭 𝒂𝑰𝑰 𝑯𝑪𝒍
• The electronic current passes from the anode (left side) to the cathode (right side).
• The Cl- ions diffuse through porous diaphragm from the region of high concentration (right side) to the region of
lower concentration (left side).
Cationic cells
K, Hg│KCl (𝒂II) | KCl (𝒂I) │K, Hg
If aI > aII, the K(Hg) electrode on the left side which is in contact with the lower K+ concentration is the anode.
K ⇌ K+ (II) + e
the K(Hg) electrode in the right side which is in contact with the higher K+ concentration is the cathode.
K+ (I) + e ⇌ K
And the overall reaction is:
K+ (I) ⇌ K+ (II)
Then we have the emf as:

𝑹𝑻 𝒂𝑰 𝑲𝑪𝒍
𝑬= 𝒍𝒏
𝑭 𝒂𝑰𝑰 𝑲𝑪𝒍
 Ion-selective electrodes and bio-membranes
• If it were possible to have an interface permeable to only one ion (say H+), then the transport
number of that ion would be unity and

RT 𝑎𝐻𝐼+
𝐸𝑗 = ln
𝐹 𝑎𝐻𝐼𝐼+
or, in general, for an ion (i) of charge z,

RT 𝑎𝑖𝐼
𝐸𝑚 = ln
𝑧𝑖 𝐹 𝑎𝑖𝐼𝐼
• The corresponding liquid junction potential (𝐸𝑚 )is called the membrane potential.
• Ideally (𝐸𝑚 ) changes in a Nernstian fashion with the activity of the ion in one of the phases,
the activity in the other phase being held constant.
• This is the basis of the functioning of ion-selective electrodes and bio-membranes.
Electrolyte concentration cells According to Nernst equation:
Zn, Zn2+(𝒂+)1 || Zn2+(𝒂+)2 , Zn ER  E 0 
RT
ln
1
 E0 
RT
ln(a ) 2
nF (a ) 2 nF
RHE: Zn2+(𝒂+)2 + 2e⇌ Zn(s) RT 1 RT
EL  E 0  ln  E0  ln(a )1
LHE: Zn(s) ⇌ Zn2+(𝒂+)1 + 2e nF (a )1 nF
RT (a ) 2
Overall: Zn2+(𝒂+)2 ⇌ Zn2+(𝒂+)1 ECell  ER  EL  ln
nF (a )1
Substituting activity by molality (m1 and m2) and activity coefficient ( )
Then we have the emf as:

RT  2 m2
E ln
2F  m
1 1
 Consider a cell consisting of two cells connected back to back
Electrolyte concentration cells
through silver electrodes:
Pt, H2(g) 1 atm , H+(𝒂+)1 || H+(𝒂+)2 , H2(g) 1 atm, Pt
Pt, H2(g) , HCl(𝒂1), AgCl, Ag| Ag, AgCl, HCl(𝒂2), H2(g), Pt
RHE: H+(𝐚 +)2 + e ⇌ ½ H2(g)
RHE: Ag + H+(𝐚2) + Cl-(𝐚2) ⇌ ½ H2(g) 1 atm + AgCl(s)
LHE: ½ H2(g) ⇌ H+(𝐚+)1 + e
LHE: ½ H2(g) 1 atm +AgCl(s) ⇌ Ag + H+(𝐚1) + Cl-(𝐚𝟏)
Overall: H+(𝒂+)2 ⇌ H+ (𝒂+)1
Overall: H+(𝐚2) + Cl-(𝐚2) ⇌ H+(𝐚1) + Cl-(𝐚𝟏)
Then we have the emf as:
Then the emf is:
RT 1 RT ECell  ER  EL
ER  E 0  ln  E0  ln(a ) 2
nF (a ) 2 F RT 1 RT 1
ER  E 0  ln  (E0  ln )
RT 1 RT F (aH  ) 2 (aCl  ) 2 F (aH  )1 (aCl  )1
EL  E 0  ln  E0  ln(a )1
nF (a )1 F 2
RT (aH  ) 2 (aCl  ) 2 RT (a ) 2 (a ) 2
2

RT (a ) 2 EL  ln  ln
ECell  ER  EL  ln F (aH  )1 (aCl  )1 F (a )1 (a )1
F (a )1 2 RT (a ) 2
ECell  ER  EL  ln
F (a )1

( a ) are the mean ionic activities of the HCl solutions in the two
cells.
 Concentration Cells with Transference
Consider a concentration cell formed by
combining two hydrogen gas elecctrodes in
contact with HCl solutions of different
concentrations. The two solutions are in direct
contact with each other as shown:
Pt, H2(g) , HCl(𝒂1) | HCl(𝒂2), H2(g), Pt
H+ →
← Cl-
LHE: ½ H2(g) ⇌ H+(𝐚+)1 + e …1
RHE: H+(𝐚+)2 + e ⇌ ½ H2(g) …2
Let t- be transport number of Cl- and t+ (= 1-t- ) be that
of H+ ion in HCl.
For one Faraday of electricity passing through, t-
faraday will be carried by Cl- ions and t+ faraday will
be carried by H+ ions.
As per Faraday’s II Law, t- equivalent of Cl- ions will be
transferred from the solution of activity a2 to the
solution of activity a1. This may be represented as
t- Cl- (a-)2 ⇌ t- Cl- (a-)1 … 3
At the same time t+ equivalent of H+ ions will be
transferred from the solution of activity a1 to the
solution of activity a2. This may be represented as
t+ H+ (a-)1 ⇌ t+ H+ (a-)2 … 4
The net result for the flow of one faraday of electricity is summed
up:

LHE:

Gain of 1 gram equivalent of H+ ions by process (1)

Loss of t+ gram equivalent of H+ ions by process (4)
Thus, for one Faraday of electricity, there
Net gain of H+ ions = ( 1 - t+ ) gram equivalent = t_ gram equivalent is net transfer of t- gram equivalent of H+
At the same time, ions and t_ gram equivalent of Cl- ions
from right to left. (From solution in which
Net gain of Cl- ions = t_ gram equivalent by process (3) activity of HCl is a2 to a1)
RHE:
These changes are represented as
Loss of 1 gram equivalent of H+ ions by process (2) t- H+ (a+)2 ⇌ t- H+ (a+)1
Gain of t+ gram equivalent of H+ ions by process (4) t- Cl- (a-)2 ⇌ t- Cl- (a-)1

Net loss of H+ ions = ( 1 - t+ ) gram equivalent = t_ gram equivalent

At the same time,

Net loss of Cl- ions = t_ gram equivalent by process (3)

 RT (a ) 2 RT (a ) 2
Ew.t  t ln  t ln
F (a )1 F (a )1
2
RT ( a ) 2 RT a2
Ew.t  t ln 2
 t ln
F (a )1 F a1

RT a2
ELJ  Ew.t  Ew.o.t  (t  1) ln
F a1
 LIQUID JUNCTION POTENTIAL

The emf of a concentration cell with transference includes the

potential at the junction of the two solutions of HCl.

RT (a ) 2 El =Ew.t. – Ew.o.t.

Ew.t  2t ln
F (a )1

RT (a ) 2
Ew.o.t 2 ln
F (a )1

When the two solutions are not in contact with each other, the
liquid potential does not exist.
Electrochemistry
Numericals
1. Calculate the EMF of the electrode-concentration cell,
Hg-Zn(c1), Zn2+(aq), Hg-Zn(c2) at 25 0C, if the concentrations of
the zinc amalgam are : c1 =2 g of zinc per 100 g of mercury
and c2 =1 g of zinc per 100 g of mercury.
The half-cell reactions in this case are:
RHE: Zn2++ 2e⇌ Zn(c2)
LHE: Zn(c1) ⇌ Zn2+ + 2e

Overall: Zn2+(𝒄𝟏) ⇌ Zn2+(𝒄𝟐)

RT c2 0.0591  1 
E ln  ln   8.8 10 3V
2F c 2 2
1
2. Calculate the EMF of the electrode-concentration cell,
Pt, H2(p1), HCl, H2(p2), Pt at 25 0C, if p1 = 600 torr and p2
= 400 torr.
The half-cell reactions in this case are:
RHE: 2H++ 2e⇌ H2 (p2)
LHE: H2 (p1) ⇌ 2H++ 2e

Overall: H2 (p1) ⇌ H2 (p2)

RT p2 0.0591  400 
E ln  ln   5.19 10 3V
2F p 2  600 
1
3. Calculate the EMF of the electrode-concentration cell
consisting of zinc electrodes, one immersed in a solution of
0.01 molality and the other in a solution of 0.1 molality
at 25 0C. The two solutions are separated by a salt bridge.
The mean activity coefficient of the electrolyte may be
assumed to be unity.
The cell may be represented as:
Zn, Zn2+ (m1 =0.01) || Zn2+ (m2 =0.1) , Zn

RT a 2 0.0591  0.10 

E    0.0295V
2F
ln
a 1 2  0.01 
ln
4. Find the potential difference between the hydrogen electrodes in the
cell,
Pt, H2(g, 1 atm) , HCl(𝐦1=0.01), AgCl, Ag|| Ag, AgCl, HCl(𝐦2=0.10), H2(g, 1 atm), Pt
at 25 0C. The activity coefficient of 0.01m and 0.10 m solutions are 0.95
and 0.85 respectively.
The cell may be represented as:
H2, H+ (m1 =0.01) || H+ (m2 =0.1) , H2

RT a 2 0.0591  0.10  .85 

E    0.056V
2F
ln
a 1 1  0.01 .95 
ln
5. Calculate the liquid junction potential
at 25 0C between two solutions of HCl having mean ionic
activities of 0.01 and 0.001 respectively. The transference
number of H+ ion (t+) in HCl may be taken as 0.83.

RT a 2 0.0591  0.001 

E  (t  t )  (0.17  0.83)   0.0039V
F
ln
a 1 1
ln
 0.01 
Corrosion
Corrosion is defined as a destructive chemical or
electrochemical reaction of a metal with its environment (like
O2, CO2, moisture etc.

This process disfigures the metallic parts leading to reduction

in thickness and loss of properties such as malleability,
ductility, electrical conductivity and optical reflectivity.
Factors influencing corrosion
Types of Corrosion

• Dry or Chemical Corrosion

• Wet or Electrochemical Corrosion

- - - - - -pH < 7 - - - - - - - - -

- - - - - -pH > 7 - - - - - - - - -
Types of Corrosion
Concentration cell corrosion
Galvanic Corrosion
II. Surface coating
There are two types of surface coating:

Surface
coating

Metallic Non-metallic
coating coating

organic inorganic
coating coating

A. Metallic coating
The structure is coated with a layer of other metal which may be more noble than the structure or
less noble than it e.g. steel structures can be coated with copper which is more noble than steel or
zinc which is less noble. In case of coating the structure with a more noble metal care should be
taken that the coat is free from pores or cracks to avoid the formation of dissimilar metal
corrosion cells which would lead to corrosion of the structure.
Factors that must be considered in selection of a coating metal:
1. The coating should be able to resist direct attack of the environment.
2. The coating should be nonporous and continuous (no cracks) to a void acceleration of
corrosion especially in case of a more noble metal (ex: coating of Fe by Cu).
3. The coating should be hard.
In case of coating the structure with a less noble metal the presence of pores and cracks in the
coat is not dangerous because in this case the less noble metal will corrode by the formation of
dissimilar metal cells while the structure will remain protected.
Question: give reasons
It is preferred to coat steel with Zn rather than with Cu.
In practice metallic coating is carried out by different methods such:
(1) Electroplating,
(2) Hot dipping of the work piece in molten metal covered with a flux,
(3) Spraying of the molten metal on the work piece.

4
(1) Electroplating
 Electroplating is the method of coating one metal with another. It is most commonly used for
decorative purposes, appearance and protection.
 Electroplated items include chrome bumpers, jewelry, electronics, circuit boards and airplane
parts.

Electroplating procedure

1. Preparation of the workpiece. Solutions such as alkaline cleaners, solvent degreasers or

acidic pickling mixtures are used to remove dirt, greases, oxidation and contaminants
from the piece.
2. The piece to be plated is connected to the negative pole (cathode) of the d. c. power
supply while the plating (coating) metal anode is connected to the positive pole (anode).
Multi-range ammeter (in series) and voltmeter (in parallel) are connected to the cell to
measure the cell current and voltage.
3. The piece is then immersed in the plating solution until coated and rinsed and then buffed
or polished, if necessary.

Note: The plating time depends on the required thickness and can be calculated from Faraday’s
law.

Factors affecting coating quality:

The quality of coating depends on:

1. Average thickness of coating

2. Porosity and continuity
3. Uniformity of thickness
4. Adherence

5
 Fig. 1, Some examples for electroplating process

(2) Hot dipping of the work piece in molten metal covered with a flux
There are two common processes of hot dipping:
1. Hot dipping galvanizing
 It is a hot coating process whereby the cleaned steel is immersed in molten zinc usually at a
temperature of between 445 °C and 450 °C.
 When the cleaned steel is immersed into the molten zinc, a chemical reaction results, which
we refer to as following “metallurgical laws”.

6
  As a result of this process the coating consists of a series of zinc iron alloy layers (inter-
metallic layer) and usually a top pure zinc layer. The adhesion of the coating to the steel is
therefore determined by means of a chemical bond, or a “metallurgical bond”. Such
bonding is considered to be far superior to that of a mechanical bond.
 A hot dipped galvanized coating will provide greater corrosion protection to steel when
compared to that of an electroplated product.

Fig. 2, Hot dipping galvanizing of steel

Fig. 3, Galvanization of steel by hot dipping and electroplating

Note: Coating of steel with Zn is called galvanization. It may be carried out by hot dipping or
electroplating.

7
2. Hot-dipped tin plating
Tinning is the process of thinly coating sheets of iron or steel with tin, and the resulting product
is known as tinplate. It is most often used to prevent rust

Tinplate made via hot-dipped tin plating is made by cold rolling steel or iron, pickling or remove
any scale, annealing to remove any strain hardening, and then coating it with a thin layer of tin.
The attached figure shows the tinning process steps.

Fig. 4, Basic concept of hot dipped tin plating process

Advantage of hot dipping process

 No waste from production process.
 No hazardous substance (such as cyanogens, lead, etc.) is used at all in production process.
 The coating metal and the base metal are strongly bonded as inter-metallic layer formed.
 Provide greater corrosion protection to steel when compared to that of an electroplated
product.

8
(3) Spraying of the molten metal on the work piece.
 Thermal spraying refers to a process by which a metal wire or powder is melted and
sprayed onto a surface to form a coating.
 A thermal spray gun is used to apply the coatings.
 The thermal spray gun heats the metallic wire or powder to a molten state and compressed
air or other gas propels it onto the surface to form a coating. The compressed gas also aids
in division and atomization of the molten coating.
 The two metals most commonly applied by thermal spray are zinc and aluminum. These
metals and their alloys provide excellent protection in a variety of marine and industrial
corrosive environments.

Questions:

1. Sketch a simple cell for galvanization of steel one by electroplating and one by hot dipping
2. What are the advantages of hot dipping when compared with electroplating as a method for
metallic coating?
3. What are the main factors that should be considered when selecting a coating metal and what
are the main factors affecting the coating quality?
4. Explain the main steps involved in electroplating process with the help of simple sketch.
5. Why it is preferred to coat steel with zinc rather than with copper.

Non-metallic coating (the second method of surface coating)

There are two types of nonmetallic coating:

A. Inorganic coating

Methods of inorganic coating:

i. Oxidation (passivation)

Steel can be coated with an oxide film by a). Heating at high temperature, b). Chemical oxidation
by treating steel with hot alkaline nitrate, or persulphate or perchlorate c). Anodic oxidation by
making the steel structure an anode in electrolytic cell

9
ii. Phosphating

Steel is coated with a layer of iron phosphate by dipping in a solution containing phosphoric acid
and zinc phosphate. The iron phosphate film is not highly protective because it is porous so it
usually covered with paint. The phosphate film improves the bond between the metal and the
paint.

i.e. Phosphating is a pre-painting step.

iii. Enamels

Enamels are glassy layer applied to the metal by dipping it in a suspension of powdered glass,
and then the metal is heated in a stove (furnace) at high temperature where the glass powder
melts and coat the metal.

iv. Cement coating

It is used to coat the inner side of steel pipelines carrying water or wastewater.

Fig. 5, Cement coating of the inner wall of water steel pipeline

10
B. Organic coating such as the following:
i. Paints:

Paint consists of;

1. a film forming substance such as linseed oil or a polymer (resin),

2. an organic solvent and
3. a pigment (usually an inorganic oxide or metal powder).

Before applying paint to a steel surface, the metal surface should be cleaned of oxides by sand
blasting or acid pickling. After cleaning, the metal surface is coated with a thin layer of primer.

What is primer?

A primer is a paint containing a pigment such as lead oxide (Pb3O4 red lead) or zinc chromate
which oxidizes the steel surface and inhibits its corrosion. Besides, the primer film increases the
strength of the bond between steel and final paint film. When the primer film dries a thick film of
the required paint is applied over the primer.

Polymers such as alkyd resins, PVC, polyethylene, polyesters, acrylics, polyurethanes,

chlorinated rubber, epoxy resins, etc. are used in paint manufacture. For severe conditions such
marine and industrial atmosphere, a paint containing epoxy resin (water resistant) is suitable.

ii. Lacquers:

A lacquer consists of a thermoplastic polymer dissolved in an organic solvent. Lacquers can be

used to line steel tanks holding corrosive chemicals such as acids.

iii. Coal tar

Coal tar is a brown or black liquid of extremely high viscosity. Coal tar is among the by-products
when coal is carbonized to make coke or gasified to make coal gas. Coal tars are complex and
variable mixtures of phenols, polycyclic aromatic hydrocarbons (PAHs), and heterocyclic
compounds, about 200 substances in all.

11
 It is used to protect underground structures. A 50% coal tar + 50% epoxy is superior to coal tar.

Fig. 6, Coating of outside surface of pipeline with coal tar + epoxy

iv. Temporary coating:

It is used to protect metallic structures during shipping and storage by coating the structure with
layer of lubricating oil which can be removed by an organic solvent when the structure is put to
service.

III. Corrosion Inhibitors

Required: definition, mechanism and types
 Definition of corrosion inhibitors:
Corrosion inhibitors are substances that are added in small amount (e.g 0.1%) to the corrosive
medium stop or slow down electrochemical corrosion reactions on a metal surface.
 Mechanism:
Corrosion inhibitors work by one or more of the following mechanisms.
• They adsorb on metal surfaces to form protective films.

12
 • They combine with corrosion product films to protect metal surfaces.

• They form precipitates, which visibly coat and protect metal surfaces.

Types of inhibitors:
 Inhibitors can be divided into two main categories—inorganic and organic.
 Inorganic inhibitors are used mainly in boilers, cooling towers, and fractionation units.
 Organic inhibitors are used mainly in oil field systems.
As shown in the figure, inorganic inhibitors are further divided into anodic and cathodic
classifications. These classifications describe the part of the electrochemical process that is
interrupted by the inhibitor. Organic film-forming inhibitors interrupt both the anodic and
cathodic processes.

Classification of corrosion inhibitors

Inorganic inhibitors

1. Cathodic inhibitors:
Cathodic inhibitors are chemical compounds which inhibit the cathodic reaction of the corrosion
cell.
Examples of cathodic inhibitors:-

13
a. Compounds such as ZnSO4, MgSO4 and Ca(HCO3)2, these compounds inhibit the cathodic
reaction by forming insoluble Zn(OH)2 film or Mg(OH)2 film or CaCO3 film with the
cathodically formed ions (in neutral solutions) the insoluble film isolates the cathodic
regions of the corrosion cells from the corrosive medium and stops corrosion.
b. Oxygen scavengers, these are compounds which react with dissolved oxygen and remove it
from the neutral or alkaline corrosive environment such as sodium sulphite or hydrazine (used to
inhibit boiler corrosion and are called high temperature oxygen scavengers)

Fig. 7, Oxygen depolarize the cathode

c. Compounds such as arsenic (As), mercury (Hg), antimony (Sb) salts which are added to acidic
corrosive environments to slowdown the cathodic H2 evolution reaction.

 These compounds prevent the hydrogen atoms from forming hydrogen gas, and are called
cathodic poisons.
 Cathodic poisons are used advantageously as corrosion inhibitors by stifling the cathodic
reduction processes that must balance the anodic corrosion reaction. However cathodic
poisons can also increase the susceptibility of a metal to hydrogen induced cracking since
hydrogen can also be absorbed by metal during aqueous corrosion or cathodic charging.

14
When corrosion occurs in a low-pH solution, some of the reduced hydrogen does not form
gaseous hydrogen, but instead, diffuses into the metal as atomic hydrogen and form metal
hydride causing hydrogen embrittlement.

Note:

Also substances such as sulfur, selenium, tellurium, and cyanide ions do the same effect.

2. Anodic inhibitors: Are chemical compounds which inhibit the anodic reaction of the
corrosive cells.
Examples
a. Compounds such as Na2SiO3, Na2CO3 and Na3PO4, these compounds form with the
anodically formed Fe++ an insoluble film of iron silicate or iron carbonate or iron phosphate
which isolates the anodic sites of the corrosion cells from the corrosive solution.
b. Passivators: these are oxidizing agents such as chromate inhibitors (Na2Cr2O7) or nitrite
inhibitors (NaNO2) which react with the anodically formed Fe++ to form a passive oxide film
on the anodic sites of the corrosion cells.

Chromate inhibitors are the most effective of the anodic inhibitors. They were used for many
years in cooling towers and other recirculating cooling water systems; however, they are toxic to
most organisms. Chromate inhibitors contain sodium chromate, Na2CrO4, or sodium dichromate,
Na2Cr2O7. Chromate, or dichromate, ions accept electrons that are lost in ferrous iron oxidation
reactions. This reduction reaction forms chromium (III) oxide ( . The chromium oxide
combines with iron oxide to form a mixed oxide. This combination of iron oxide and chromium
oxide makes chromium inhibitors effective. Normally, iron oxide deposits are loosely attached to
metal surfaces. However, the combination of iron oxide and chromium oxide forms a deposit that
tightly attaches to the metal surface.

(0.2%, PH =8) was used widely in industry to protect the cooling system of the plant
against corrosion. Recently chromate has been replaced by a mixture of Zn++, polyphosphate

15
and chromate which is less harmful to the environment because the mixture uses a lower doze of
the toxic . More recently zinc phosphate is being used without chromates.

Nitrite inhibitors may be used to replace the more toxic chromates. Sodium nitrite (NaNO2) is
used in closed, recirculating cooling water systems with a pH between 7 and 9. Nitrites perform
similarly to chromates. They form a protective iron oxide film that passivates steel surfaces.
Nitrites can reduce corrosion rates to less than 2 mpy. They are environmentally acceptable and
easy to monitor.

Note:

Nitrites easily oxidize to nitrates. Nitrates are not effective corrosion inhibitors. That is why
nitrites are used in closed systems.

3. Adsorption Inhibitors: (organic inhibitors)

These are organic compounds which contain a polar group such as NH2 (amino group), these
compounds (RNH2) adsorb on the metallic surface and isolate it from the corrosive solution
(usually acids).

Organic corrosion inhibitors are complex mixtures of many different molecular compounds.
Organic inhibitors typically affect both anodic and cathodic areas of corrosion cells. They lay
down an organic film on the entire metal surface. Their effectiveness depends upon the following
conditions:

 the electrical potential of the metal

 the chemical structure of the inhibitor molecule
 the size and shape of the inhibitor molecule

An organic corrosion inhibitor molecule consists of a hydrocarbon chain that is attached to a

strongly polar functional group. The hydrocarbon chain of the inhibitor molecule is oil soluble.
This chain provides a barrier that keeps water away from the metal surface. The length of the

16
hydrocarbon chain varies (e.g., carbon numbers between 12 and 18). Polar functional groups are
based on nitrogen, sulfur, or oxygen.
Most organic inhibitors used in the petroleum industry contain at least one nitrogen functional
group. Frequently, these nitrogen-based inhibitors are reacted with organic acids, or they contain
oxygen functional groups. The amine (NH2) portion of the molecule is water soluble and has a
pair of unshared electrons. These electrons are available to bond with metal surfaces.

Fig. 8, Organic inhibitor molecule

Organic inhibitor molecules attach to metal surfaces by chemisorption and physical adsorption.
When a metal is in contact with an aqueous solution, most of the metal surface is covered with
adsorbed water molecules. If an organic inhibitor is introduced into the system, the unshared
electrons in the polar amine group form a chemisorption bond with the metal surface. The
chemisorption bond displaces water molecules and other corrosive agents from the metal surface.
The long hydrocarbon chains also play an important part in the inhibition process. The
hydrocarbon chains are oil soluble and attract crude oil molecules in the process stream.
Together, the hydrocarbon chains and oil molecules form an oily layer several molecules thick.
This oily layer acts as a barrier against corrosive fluids. The oily layer also increases the film life
of the inhibitor. In addition to the chemisorption bond, organic inhibitors also physically adsorb
to the metal surface. Physical adsorption is weaker than chemisorption. Physical adsorption does
not involve a sharing of electrons with the metal surface. The figure below shows the molecular
structures of some common oil field corrosion inhibitors.
Note:
Organic inhibitor molecules can be modified to increase their solubility or dispersibility in brine.
These modifications include adding more polar groups to each inhibitor molecule. Sometimes,

17
the dispersibility of an oil soluble inhibitor is increased by blending it with a surfactant. This
blending technique helps to disperse the oil soluble inhibitor into both the oil and water phases.

Fig. 9, Molecular structure of some organic inhibitors

Questions:
Complete:
1. inorganic coating involves:
a)……………… b)……………… c)……………… d)………………
2. organic coating involves:
a)……………… b)……………… c)……………… d)………………
3. What is acid pickling and at what conditions it is used?
4. What is primer and what its function?
5. What are cathodic poisons? Give examples.
6. Why are nitrites not used in open systems as corrosion inhibitor?
7. Suggest a suitable method of corrosion protection for the following cases:
 Underground pipeline carrying wastewater
 Steel tank containing saline water
8. Give reasons:
 Chemicals such as Na2SO3 and Na2CO3 inhibit corrosion
 N2H4 is added to water feed boilers (WFB)
18
4. Electrical protection
A. Cathodic protection
Technique to reduce corrosion of a metal surface by making that surface the cathode of an
electrochemical cell.
Cathodic protection is a method to reduce corrosion by minimizing the difference in potential
between anode and cathode. This is achieved by applying a current to the structure to be
protected (such as a pipeline) from some outside source. When enough current is applied, the
whole structure will be at one potential; thus, anode and cathode sites will not exist. Cathodic
protection is commonly used on many types of structures, such as pipelines, underground storage
tanks and ship hulls.
Types of cathodic protection systems
There are two main types of cathodic protection systems:
a) Galvanic system (sacrificial anode method)
b) Impressed current method
The figures below show these two types. Note that both types have anodes (from which current
flows into the electrolyte), a continuous electrolyte from the anode to the protected structure, and
an external metallic connection (wire). These items are essential for all cathodic protection
systems.

Fig. 10, Internal cathodic protection of pipeline by sacrificial anode method

19
Fig. 11, External cathodic protection of water pipeline by sacrificial anode method

Fig. 12, Cathodic protection of water heater by sacrificial anode method

20
 Fig. 13, Cathodic protection of underground storage tank by impressed current
a) Galvanic system (sacrificial anode cathodic protection)
A galvanic cathodic protection system makes use of the corrosive potentials for different metals.
Without cathodic protection, one area of the structure exists at a more negative potential than
another, and corrosion results. If, however, a much less inert object (that is, with much more
negative potential, such as a magnesium anode) is placed adjacent to the structure to be
protected, such as a pipeline, and a metallic connection (insulated wire) is installed between the
object and the structure, the object will become the anode and the entire structure will become
the cathode. That is, the new object corrodes sacrificially to protect the structure as shown in
Figure 14 (a). Thus, the galvanic cathode protection system is called a sacrificial anode cathodic
protection system because the anode corrodes sacrificially to protect the structure. Galvanic
anodes are usually made of either magnesium or zinc because of these metals’ higher potential
compared to steel structures.

21
 Fig. 14, Galvanic (a) and impressed (b) current systems for cathodic protection
b) Impressed current systems
Impressed current cathodic protection systems use the same elements as the galvanic protection
system; only the structure is protected by applying a current to it from an anode. The anode and
the structure are connected by an insulated wire, as for the galvanic system. Current flows from
the anode through the electrolyte onto the structure, just as in the galvanic system. The main
difference between galvanic and impressed current systems is that the galvanic system relies on
the difference in potential between the anode and the structure, whereas the impressed current
system uses an external power source to drive the current, as shown in Figure 1(b). The external
power source is usually a rectifier that changes input AC power to the proper DC power level.
The rectifier can be adjusted so that proper output can be maintained during the system’s life.
Impressed current cathodic protection system anodes typically are high-silicone cast iron or
graphite.
CATHODIC PROTECTION DESIGN
Required information:
Before deciding which type, galvanic or impressed current, cathodic protection system will be
used and before the system is designed, certain preliminary data must be gathered. The following
is a list of these data.

22
1. Physical dimensions of structure to be protected
One important element in designing a cathodic protection system is the structure's physical
dimensions (for example, length, width, height, and diameter). These data are used to calculate
the surface area to be protected (affect the required current).
2. Drawing of structure to be protected
The installation drawings must include sizes, shapes, material type, and locations of parts of the
structure to be protected.
3. Electrical isolation
If a structure is to be protected by the cathodic system, it must be electrically connected to the
anode, as Figure 14 shows. Sometimes parts of a structure or system are electrically isolated
from each other by insulators. For example, in a gas pipeline distribution system, the inlet pipe to
each building might contain an electric insulator to isolate in-house piping from the pipeline.
Also, an electrical insulator might be used at a valve along the pipeline to electrically isolate one
section of the system from another. Since each electrically isolated part of a structure would need
its own cathodic protection, the locations of these insulators must be determined.
4. Short circuits. All short circuits must be eliminated from existing and new cathodic
protection systems. A short circuit can occur when one pipe system contacts another, causing
interference with the cathodic protection system. When updating existing systems,
eliminating short circuits would be a necessary first step.
5. Corrosion history of structures in the area
Studying the corrosion history in the area can prove very helpful when designing a cathodic
protection system. The study should reinforce predictions for corrosivity of a given structure and
its environment; in addition, it may reveal abnormal conditions not otherwise suspected.
Facilities personnel can be a good source of information for corrosion history.
6. Electrolyte resistivity survey
A structure's corrosion rate is proportional to the electrolyte resistivity. Without cathodic
protection, as electrolyte resistivity decreases, more current is allowed to flow from the structure
into the electrolyte; thus, the structure corrodes more rapidly. As electrolyte resistivity increases,
the corrosion rate decreases (Table 2). Resistivity can be measured either in a laboratory or at the
site with the proper instruments. The resistivity data will be used to calculate the sizes of anodes
and rectifier required in designing the cathodic protection system.

23
 Table (2) Corrosivity of soils on steel based on steel resistivity
7. Electrolyte pH survey
Corrosion is also proportional to electrolyte pH. In general, steel's corrosion rate increases as pH
decreases when soil resistivity remains constant.
8. Structure versus electrolyte potential survey
For existing structures, the potential between the structure and the electrolyte will give a direct
indication of the corrosivity. According to NACE Standard No. RP-01, the potential requirement
for cathodic protection is a negative (cathodic) potential of at least 0.85 volt as measured
between the structure and a saturated copper-copper sulfate reference electrode in contact with
the electrolyte. A potential which is less negative than -0.85 volt would probably be corrosive,
with corrosivity increasing as the negative value decreases (becomes more positive).
9. Current requirement
A critical part of design calculations for cathodic protection systems on existing structures is the
amount of current required per square foot (called current density) to change the structure’s
potential to -0.85 volt. The current density required to shift the potential indicates the structure's
surface condition. A well coated structure (for example, a pipeline well coated with coal-tar
epoxy) will require a very low current density (about 0.05 milliampere per square foot); an
uncoated structure would require high current density (about 10 milliamperes per square foot).
The average current density required for cathodic protection is 2 milliamperes per square foot of
bare area. The amount of current required for complete cathodic protection can be determined
three ways:

 An actual test on existing structures using a temporary cathodic protection setup.

 A theoretical calculation based on coating efficiency.
 An estimate of current requirements using tables based on field experience.
The second and third methods above can be used on both existing and new structures.

24
Current requirements can be calculated based on coating efficiency and current density (current
per square foot) desired. The efficiency of the coating as supplied will have a direct effect on the
total current requirement, as Equation 1 shows:
(1)
where
I: is total protective current,
A: is total structure surface area in square feet,
i: is required current density,
and CE: is coating efficiency.
Equation 1 may be used when a current requirement test is not possible, as on new structures, or
as a check of the current requirement test on existing structures. Coating efficiency is directly
affected by the type of coating used and by quality control during coating application.
Note:
The importance of coating efficiency is evident in the fact that a bare structure may require
100,000 times as much current as would the same structure if it were well coated.
Current requirements also can be estimated from Table 2. The table gives an estimate of current,
in milliamperes per square foot, required for complete cathodic protection. That value, multiplied
by the surface area of the structure to be protected (in square feet) gives the total estimated
current required. Caution should be used when estimating, however, as under- or overprotection
may result.

Table 3, Typical current density requirements for cathodic protection of uncoated steel

25
10. Coating resistance
A coating's resistance decreases greatly with age and directly affects structure-to-electrolyte
resistance for design calculations. The coating manufacturers supply coating resistance values.
11. Protective current required
By knowing the physical dimensions of the structure to be protected, the surface area can be
calculated. The product of the surface area multiplied by current density obtained previously
gives the total current required.
12. The need for cathodic protection
For existing structures, the current requirement survey (above) will verify the need for a cathodic
protection system. For new systems, standard practice is to assume a current density of at least 2
milliamperes per square foot of bare area will be needed to protect the structure. (However, local
corrosion history may demand a different current density.) In addition, cathodic protection is
mandatory for underground gas distribution lines and for water storage tanks with a 250,000-
gallon capacity or greater. Cathodic protection also is required for underground piping systems
located within 10 feet of steel reinforced concrete because galvanic corrosion will occur between
the steel rebar and the pipeline.

26
Determining type and design of cathodic protection system
When all preliminary data have been gathered and the protective current has been estimated, the
design sequence can begin. The first question to ask is: which type (galvanic or impressed
current) cathodic protection system is needed?
The criterion used most widely is based on current density required and soil resistivity.
A galvanic system can be used at the following conditions:
1. If the soil resistivity is low (less than 5000 ohm-centimeters) and
2. The current density requirement is low (less than 1 milliampere per square foot).
However, if the soil resistivity and/or current density requirement exceed the above values, an
impressed current system should be used.
a. Sacrificial anode (galvanic) cathodic protection system design
The following steps are required when designing galvanic cathodic protection systems:
1. Review soil resistivity.
The site of lowest resistivity will likely be used for anode location to minimize anode-to-
electrolyte resistivity. In addition, if resistivity variations are not significant, the average
resistivity will be used for design calculations.
2. Select anode
Galvanic anodes are usually magnesium, Aluminum or zinc.
Anode specification will include:
 anode weight  anode dimensions
 and package dimensions(anode plus backfill)
Table 4 shows for magnesium-alloy anodes.

Table 4, specifications for Mg alloys anodes

27
Notes:
 Zinc anodes are used in extremely corrosive soil (resistivity below 2000 ohm-
centimeters).
 The choice of anode from those available is arbitrary; design calculations will be made
for several available anodes, and the most economical one will be chosen.

Notes about backfill

Backfill material:

It is a material used to reduce the groundbed resistance

The type of backfill used in a groundbed depends on whether the cathodic protection system is
sacrificial or impressed.

 Chemical backfills:
The chemical backfill used with galvanic anodes provides an environment which is conducive
for anode dissolution. A typical mixture is 75% powdered gypsum (calcium sulfate), 20%
granular bentonite and 5% sodium sulfate. This mixture has a resistivity of 50 (Ω · cm) and is
suitable for use in high resistivity soils. The function of the bentonite is to absorb water and
expand, thus ensuring good contact between anode and soil by lowering groundbed resistance. A
75% bentonite 25 % gypsum mixture (250 Ω · cm) is recommended for low moisture soils.
 Carbonaceous backfills:
Impressed current anodes are usually surrounded by a carbonaceous backfill. Types of materials
use include coke breeze, calcined petroleum coke and natural graphite.
The backfill serves three basic functions: (a) it decreases the anode-to-earth resistance by
increasing the anode’s effective size, (b) it extends the system’s operational life by providing
additional anode material, and (c) it provides a uniform environment around the anode,
minimizing deleterious localized attack.
To ensure good electrical contact, the backfill must be tamped around the anode. Resistivity of
carbonaceous backfills is in the order of 50 Ω cm.
3. Calculate net driving potential for anodes
The anode is coupled with a reference electrode (copper-copper sulfate) to measure its
potential. The potential of iron (The structure to protected) in contact with soil or water

28
usually ranges around -0.55 to -1 volt relative to copper-copper sulfate. For practical approach
consider iron polarized to -0.85 volt.
Accordingly the net driving potential for the anode will be:

4. Calculate the total resistance of the galvanic cell

The total resistance is calculated from the equation:

where:
 : is the total resistance  : is the anode to electrolyte resistance
 : is the wire resistance  : is the cathode to electrolyte resistance

: is the net driving potential for anode

I: is the protection current

: is the average coating resistance per unit area at the end of the proposed lifetime (R is
specified by the supplier)
A: is the structure’s surface area
is negligible

5. Calculate the number of anodes needed

The number of anodes should fulfill the following:
a. Should meet groundbed resistance
The number of anodes needed to meet the groundbed resistance is calculated from the
equation:

where:
: is the soil resistivity in ohm.centimeter
L: is the length of the backfill column, ft

29
d: diameter of backfill column, ft (L and d are specified by the supplier)
b. Should meet system’s life expectancy
Each cathodic protection system will be designed to protect a structure for a given number
of years. The number of anodes that should be used to protect the structure for a period n
is given by the equation:

where:
is the number of years the structure will be protected
is the current density required to protect the structure milliampere/square feet
is the weight of one anode in pounds
There are two values for N now. How to select N?
The greater value of the above two equations will be used as the number of anodes needed
for the system.
6. Select groundbed layout
When the required number of anodes has been calculated, the area to be protected by each
anode is calculated by the equation:

7. Calculate the life cycle cost for proposed design

The design process should be done for several different anode choices to find the one with
minimal life cycle cost.
b. Impressed current cathodic protection system design
When designing impressed current cathodic protection systems the following steps are required.
1. Review soil resistivity
As with galvanic systems, this information will contribute to both design calculations and
location of anode groundbed.
2. Review current requirement test
The required current will be used throughout the design calculations. The calculated current
required to protect 1 square foot of bare pipe shall agree with the values in Table 3.

30
3. Select anode
As with the galvanic system, the choice of anode is arbitrary at this time; economy will
determine which anode is best. Table 5 gives common anode sizes and specifications. The
anodes used most often are made of high-silicon chromium-bearing cast-iron (HSCBCI). When
impressed current-type cathodic protection systems are used to mitigate corrosion on an
underground steel structure, the auxiliary anodes often are surrounded by a carbonaceous
backfill. Backfill materials commonly used include coal coke breeze, calcined petroleum coke
breeze, and natural graphite particles.

Table 5, weights and dimensions of selected circular high silicon chromium bearing cast iron anodes
4. Calculate number of anodes needed
a. The number of anodes needed to satisfy manufacturer's current density limitations
Impressed current anodes are supplied with a recommended maximum current density.
Higher current densities will reduce anode life. To determine the number of anodes needed to
meet the current density limitations, use the equation:

where:
I: is the total protection current
A: is the anode surface area in square feet per anode
: is the recommended maximum current density output in milliamperes/square feet
b. The number of anodes needed to meet design life requirement
The following equation is used to find the number of anodes needed to meet design life
requirement:

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where:
is the number of years the structure will be protected
is the current density required to protect the structure milliampere/square feet
is the weight of one anode in pounds
c. The number of anodes needed to meet the maximum anode groundbed resistance
requirements
The number of anodes is calculated from the equation:

where:
is the anodes’ resistance in Ohm
is soil resistivity in Ohm. Centimeter
is the anode shape factor (from table 6)
is the number of anodes
is the length of the anode backfill column in feet
is the paralleling factor (from table 7)
is the center to center spacing between anode backfill column in feet

Table 6, shape factor as a function of L/d

Table 7, Paralleling factor as a function of N

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Now we have three equations to get N. The highest number calculated by the above three
equations will be the number of anodes used.
5. Calculate the total circuit resistance (as mentioned before)

6. Calculate the rectifier voltage and select the rectifier that satisfy the required I and V

Note: 1.5 is a safety factor to allow for aging the rectifier stack
7. Calculate the system cost and repeat steps for different anodes to choose the system of
the minimum cost
B. Anodic Protection:
It is based on the phenomenon of passivity. To understand how the anodic protection is carried
out the phenomenon of passivity should be explained first.

Consider a metal M acting as an anode in electrolytic cell. If the anode potential is increased
gradually the metal M starts to dissolve at a potential e1 given by:
MM++ +2e
e1 = eo – RT/ZF ln[M++]
At the point A current starts to flow in the cell as a result of metal dissolution, with increasing
the anode potential the current increases till the point B is reached, after this point any further
increase in the anode potential result in a decrease of the current from B to C owing to the

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formation of an oxide film on the metal surface which prevents its dissolution. Oxide film
formation takes place at the potential e2 which is given by the equation:
M + H2O MO + 2H+ + 2e
e2 = eo – RT/ZF ln[H+]2
With further increasing the anode potential no current flows through the cell until the potential e3
is reached at point D where oxygen evolution starts to evolve according to the reaction
O2 + H2O + 4e
e3=eo – RT/ZF ln[ ]4
At point D the current increases again with increasing anode potential as represented by the part
DE.

Anodic protection is carried out by connecting the structure to be protected to the positive pole of
an external d.c power supply, an auxiliary cathode made of corrosion resistant material is used to
complete the circuit. The anode potential of the structure is adjusted to be in the passive region
i.e the region represented by the area BCDE on the passivity curve. Under this condition the
structure will be coated with a layer of oxide which protects it against corrosion.
Limitation of anodic protection:
1. Anodic protection can be used only with metals which exhibit the phenomenon of passivity
such as steel, stainless steel, nickel and its alloys, chromium and its alloys, Al and Ti and their
alloys, anodic protection cannot be used with metals such as Cu and Zn and their alloys.
2. Anodic protection cannot be used when the electrolyte contains chloride ions because chloride
ions attack the oxide film and destroy it.

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5- Minimizing corrosion by proper design
The following are examples of how proper equipment design can reduce corrosion
1. Avoid dissimilar metal contact in the presence of an electrolyte especially when the
cathode/anode ratio is high such as the following example:

If the use of dissimilar metals is unavoidable in building the structure they should be separated
by an insulator such as plastic or rubber as shown by the following example:

Dissimilar metals are sometimes used intelligently to design structures which are corrosion
resistant and less expensive as shown by the following examples:

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Cooper tubes are used in building heat exchangers because copper has the highest thermal
conductivity among all metals. Other parts of the heat exchanger such as the shell, tube sheet and
head are made of steel not copper to lower the capital costs of the heat exchanger. The use of
steel offers also the advantage of protecting copper tube against corrosion by cathodic protection
through the cell: Fe/electrolyte/Cu.
Example 2 shows a centrifugal pump made of three different materials chosen to produce
inexpensive corrosion resistant efficient pump where the steel body protects the other parts of the
pump against corrosion by cathodic protection.
2. It is better from the corrosion point of view to join different sections by welding rather than
riveting to avoid crevice corrosion. After welding the heat affected zone (H.A.Z) should be
post weld heat treated (P.W.H.T) to eliminate residual stresses which may lead to corrosion.
[Crevice = clearance or gap between two surface in contact]

3. Avoid erosion-corrosion (impingement corrosion) by doubling the thickness of the parts

subjected to high degree of turbulence (high shear stress) or subjected to flowing solutions
which contain suspended solids such as tube inlets, elbows, bends, impellers of agitated
vessels, etc.

High turbulence may damage the protective oxide film on the metal and increase the rate of bare
metal corrosion by increasing the rate O2 transfer from the solution bulk to the metal surface.

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4. Avoid vibration of equipment as far as possible. Vibration increases the rate of O2 transfer
from the solution bulk to the corroding surface with a consequent increase in the rate of steel
corrosion.
Vibration leads also to corrosion fatigue. Metallic objects subjects to cyclic stresses (e.g.
vibrations) undergoes failure at a stress below the ultimate tensile stress of the metal especially
in the presence of corrosive solutions, the stress at which failure takes place decreases with
increasing the number of cycles per second as shown in the following figure.

5. Dry your equipment (e.g packed columns pipelines, etc) after testing or cleaning by passing
dry N2. Leaving this equipment wet for a long time before operation leads to serious
corrosion.
6. Design tanks for easy drainage as shown below.

Resting the tank on the floor leads to crevice corrosion of the bottom (through a differential
aeration cell). Residual solution in the tank resulting from poor drainage leads to serious
corrosion of the lower part of the tank because of the high rate of O2 diffusion through the thin
residual liquid layer left at the tank bottom.

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7. Avoid stresses in the structure
As mentioned before residual stresses left in the structure during fabrication leads to stress
corrosion cracking of the metal if used in contact with certain electrolyte. Stress corrosion
cracking can be avoided by either removing of residual strains from the metal by annealing or
avoiding contact between the metal and electrolytes to which it is sensitive.
Stresses may be also induced in heat exchanger tube if the thermal gradient across the tube wall
is high (dT/dx) where dT is the difference in temperature across the tube wall and dx is the
thickness of the wall.
Factors affecting the rate of corrosion
In view of the importance of steel as a material of construction its corrosion will be used to
illustrate the factors affecting the rate of corrosion.
1. Effect of temperature
 In the pH range 4-10 where O2 reduction is the cathodic reaction of the corrosion cell, the
rate of corrosion increases with increasing solution temperature up to 80 ᵒC and then the rate
of corrosion decreases with further increase in temperature.
 The decrease in the rate of corrosion beyond 80 C is attributed to the decrease in O2
solubility in water.
 In acid medium where the cathodic reaction of the corrosion cell is H 2 evolution, the rate of
corrosion increases with increasing temperature according to Arrhenius equation:

r = rate of corrosion; A = constant; E = activation energy; R = gas constant; T = temperature

Effect of temperature on the rate of corrosion

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2. Effect of pH

In the pH range 4 – 10 the cathodic reaction of the corrosion cell is O2 reduction i.e. in this range
of pH the rate of corrosion depends on the rate of O2 diffusion to the cathodic sites of the
corrosion cells and not the pH.
Below pH = 4 the rate of corrosion increases with decreasing the pH (increasing acidity) as the
cathodic reaction becomes H2 evolution instead of O2 reduction. At pH higher than 10 the rate of
corrosion decreases with increasing pH and steel becomes coated with a protective oxide film.
3. Effect of solution stirring
 If the cathodic reaction of the corrosion cell is oxygen reduction (pH 4-10) the rate of
corrosion increases in general with increasing the degree of stirring owing to the increase in
the rate of transfer of dissolved O2 from the solution bulk to the steel surface.
 If the cathodic reaction is H2 evolution (pH < 4) stirring has no effect on the rate of
corrosion because the reaction is chemically controlled (i.e not diffusion controlled as in
the case of O2 reduction)
4. Effect of metallurgical factors
 As mentioned before in the pH range 4-10 the cathodic reaction of corrosion cells is O2
reduction, the rate of this reaction depends on the rate of transfer of dissolved O2 from the
solution bulk to the surface of the corroding metal. Accordingly in the pH range 4-10 the
rate of corrosion does not depend on the composition of the steel or its heat treatment.

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  In acid solution (pH < 4), the cathodic reaction of the corrosion cell is H2 evolution, this
reaction is chemically controlled i.e its rate depends on nature of the metallic surface and
its composition.
 Pure iron dissolves slowly in acids while impure iron containing impurities such as P, N, S
and C dissolves rapidly because these impurities form nobler phase with iron on which H2
evolution is fast.
 On the other hand addition of Ni and Cr to iron decreases its rate of dissolution in acids.
5. Effect of dissolved salts

a. NaCl: the rate of corrosion of steel increases with increasing NaCl concentration up to a
certain point and then decreases with further increase in salt concentration
 The initial increase in the rate of steel corrosion is attributed to the increase in solution
conductivity with increasing NaCl concentration.
 The decrease in the rate of corrosion at high NaCl concentration is attributed to the
decrease in the amount of dissolved oxygen [NaCl salt out O2, the phenomena is known
as salting out].
b. Acidic salts such as NiSO4, AlCl3, NH4Cl, FeCl2, MnCl2, etc these salts produce acidic
solutions because of hydrolysis. Steel dissolves in these solutions with H2 evolution
especially in concentrated solutions.
c. Alkaline salts such as Na2SiO3, Na3PO4, Na2CO3 and Na2B4O7 (Borax), these salts produce
alkaline solutions because of hydrolysis. Under this condition these salts form an insoluble

40
 iron salt on steel surface which acts as a diffusion barrier and inhibit corrosion. Alkalinity
also favors the formation of a protective oxide film on steel.
d. Oxidizing salts such as FeCl3, CuCl2, HgCl2 and NaOCl and oxidizing salts such as
Na2Cr2O7, NaNO2 and KMnO4.

The first group of salts is highly corrosive (contain chloride ions) while the second groups
oxidizes the steel surface and inhibit its corrosion.

e. Water

Water can be divided into soft and hard water.

Hard water which contains cations such as Mg++, Ca++ is less corrosive than soft water because
Mg++, Ca++ combine with the cathodically formed to form an insoluble film of Ca(OH)2 or
Mg(OH)2 which blocks the cathodic sites of corrosion cells and inhibit corrosion.

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 Polarization

 Definition
 Types of polarizations
 Comparison
 Effect of polarization on rate of corrosion.

Any electrochemical (reaction) process takes place through two main steps, namely;

1. Diffusion step [Physical]

2. Chemical reaction [Chemical]

The speed of the reaction is controlled by the slowest step and the reaction is said to be retarded
or polarized.

Definition of polarization:

Retardation of an electrochemical reaction due to the slowness of diffusion or charge transfer

step (electron transfer).

Types of polarization:

1. Concentration polarization

This type appears when the diffusion step is the controlling step and is defined as the retardation
of an electrochemical process due to the slowness of diffusion step.

2. Activation polarization

This type appears when the chemical reaction step is the controlling step and is defined as the
retardation of an electrochemical process due to the slowness of the charge transfer step.

Comparison between concentration and activation polarization:

Concentration polarization is sensitive to stirring or agitation while activation polarization is

insensitive to stirring or agitation increase stirring and decrease concentration polarization.

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Relation between polarization and rate of corrosion:

As the magnitude of polarization increase the rate of corrosion decrease.

Passivity

Definition:

Loss of chemical activity under particular specific conditions (oxidizing solution). It is displayed
by some metals as Cr, Fe, Ni, Ti

Reasons of passivity

The passive behaviour of these metals is resulted from the formation of highly adherent and very
thin oxide film on the metal surface. This film acts as a protective barrier to further corrosion.
This is why stainless steel resists corrosion.

N.B. The passivity appears in a specific environment at specific condition.

Factors affecting passivity:

1. Type of metal or alloy 2. Type of environment

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